Low viscosity vinyl polymer



Patented 9, 1934 PATET 1,942,531 LOW vIscosrrY VINYL POLYMER Harold J. Barrett, Wilmington, DeL, assignor to E. I. (in Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application June 3, rest Serial No. 459,105

11 Claim.

This invention relates to new compositions of matter. It relates more specifically to synthetic resins, and has particular reference to resins prepared by the polymerization of vinyl compounds. Still more particularly this invention relates to means for controlling the viscosity of these resins.

The preparation of synthetic resins, particularly those oi the type derived from the polymerization of vinyl compounds, has been attended in the past with uncertainty. Those batches of polymer which had excellent color and high yield would often have viscosity so high as to make their use in finishes or in coating compositions diiilcult. Other batches made under apparently identical conditions would have good viscosity but would be very dark in color and would be produced only in low yields. The reason for these variations has previously not been understood, and has resulted in inability to secure a uniform product having good color and a viscosity suitable for the purposes to which it would be put.

Finis invention has as an object the production of new compositions of matter. Another object is the production in good yield of resins hav ing suitable viscosity and excellent color. A further object of the invention is the production oi resins, by the polymerization of vinyl compounds, which are suitable for use in plastics and coating compositions and in such other arts as resins find utility.

These cbiects, broadly speaking, are accoxn plished by polymerizing the film-forming materials in the presence of a small amount of a temene-lilze substance, such as resin, or of a rosin erivative, such as ester I have discovered that the previous inability to obtain products having uniform viscosity from different batches of raw materials can be overcome, and a uniform product of excellent viscosity characteristics can be obtained by mixing rosin th the raw materials prior to the polymerizetion of the resin.

It has been discovered that acids used in the some way as rosin accomplish the lowering of the viscosity of the final product, but I have discovcred that, although rosin consists largely of abietic acid, it does not function in this respect wholly as an acid. This is illustrated by the fact that, although abietic acid is a weaker acid than acetic acid, yet rosin causes a greater decrease in viscosity than does acetic acid. Substances like ester gum accomplish the same result as rosin. Furthermore, my invention is not limited to rosin and its derivatives, but can be attained by the use of terpene-like substances such as g. toluene,

Example "I A mixture of 2400 a. vinyl chloride, 160d 3. toluene, 36 g. rosin, and 96 g. benzoyl peroxide was passed through an eight-footlead-lined reaction tube having a capacity of too cc. at a rate of 1000 cc. per hour, under a pressure of 500 lbs. per sq. in. and. at a temperature of lilo-110 C. The solution obtained by this process weighed 1696 g., contained 33.8% solids (indicating a yield of d5.8%), and was light colored. A li% solution of the product had a viscosity less than 0.5 poise at 25 6., whereas a solution of polymer prepared from the samesample of vinyl chloride but in the absence of rosin, was a gel at this con centration.

Example H A solution containing 712 a. vinyl chloride, on l l g. ester gum, and 29 g. benzoyl per oxide was passed through a icon-toot, lead-lined reaction tube of about 500 cc. capacity at "a rate of 300 cc. per hour, under a pressure of too lbs. per sq. in. and at a temperature of i1-il5 C. The solution of polymer obtained'by this process weighed s25 g., contained 39.4% solids (indicating a yield of il.l%) and has a viscosity less than 0.5 poise at 25 Example HI A mixture of 2%20 g. vinyl chloride, cos g. vinyl acetate, to g. rosin, 90 g. bensoyl peroxide, and 1970 g. toluene was passed through an eight ioot reaction tube having a capacity of 800 cc. at 105- 110' C. under a pressure of 500 lbs. per sq. in. Analysis showed that the solution obtained by this process weighed 3551 g., contained 37.4% solids (indicating a yield of 422.2%). and had a viscosity of 0.5 poise at 25 C.

Example IV A solution containing 207 g. styrene, l2 s. rosin, and 343 g. ethyl benzene was heated at 110-120 C. for "12 hours. The ethyl benzene and unpolymerized styrene were then removed by steam dis-- tillation; leaving 153 g. oi resinous product, which indicated a yield of 83.1%. Solutions'of the prodlid loo

not hadlower viscosity characteristics than those of meta styrene prepared under the same conditions but without the rosin.

Example V I Parts Aromatic hydrocarbon-soluble polymer of vinyl chloride prepared in the presence of r 26.30 Dibutyl phthalate 2.64 Toluene 47.38 solvent naphtha 23.68

This lacquer, which had a viscosity of less than 0.4 poise at 20 C.,' gave films which became hard within 18 hours at ordinary temperatures.

Example VI Parts Aromatic hydrocarbon-soluble polymer of vinyl chloride prepared in the presence of This eel had a viscosity oi about 0.4 poise at 20 C. and had excellent spraying characteristics. Films prepared from it became hard within 18 hours at ordinary temperatures.

Emmple VII Parts Aromatic hydrocarbon-soluble polymer of vinyl chloride prepared in the presence of rosin 28.60 Dibutyl phthalate 2.87 Chrome orange 12.31 Toluene 37.50 Solvent naphtha 18.72

This orange enamel had a viscosity of about 0.4

poise at 20 C. and gave films which became hard within 18 hours at ordinary temperatures.

The temperatures recited in the specific examples have been chosen for convenience and do not illustrate limitations. Temperatures considerably higher and considerably lower can be used with satisfactory results. For instance, Example I was carried out at 130 C. with satisfactory results.

The polymerization of the substances to which rosin has been added may take place either in a continuous flow process or in a batch process.

With certain resins which have a tendency to darken during this treatment, a satisfactory color may be maintained with anti-darkening agents such as ethylene oxide.

Anadvantage of this invention is that it furnishes means for controlling the viscosity of polymerized vinyl derivatives. Another advantage is the preparation of new compositions of matter from polymerized vinyl derivatives and terpenelike substances such as rosin. Another advantage is that the preparations are suitable for highbuild coating compositions, that is, coating compositions having a high percentage of fl1m-iorm ing constituents in relation to solvent at working viscosities.

As many apparently widely different embodiments of this invention may be made without de-' parting from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. The method of making a composition of matter which comprises passing a solution containing vinyl chloride, toluene, benzoyl peroxide, and rosin, under a pressure of about 500 pounds per square inch, through a lead-lined reaction tube heated to a temperature between about 105 and about 130 C.

2. The method of making a composition of matter of matter which comprises passing a solution containing a. vinyl ester, a solvent for the vinyl ester, an organic peroxide catalyst, and rosin, under pressure, through a lead-lined reaction tube heated to a temperature of about 115 C.

3. The method of making a composition of I matter which comprises heating under pressure a solution containing one of a group of compounds consisting of vinyl esters and styrene, an organic peroxide catalyst, and one of a group of compounds consisting of rosin and rosin esters.

4. The method of making a composition of matter which. comprises polymerizing a vinyl compound of the group consistingof vinyl esters and styrene in the presence of one of a group of compounds consisting of rosin and rosin esters.

5. The product of the polymerization of a vinyl compound of the group consisting of vinyl esters and styrene in the presence of one of the group of compounds consisting of rosin and rosin esters.

6. The product of the polymerization of a viny' compound of the group consisting of vinyl esters and styrene in the presence of rosin.

l. The product of the polymerization of vinyl chloride in the presence of rosin.

8. The product of the polymerization of styrene in the presence of rosin.

9. The method of making a composition of matter which comprises heating a solution containing vinyl chloride, vinyl acetate, and rosin under pressure at a temperature of about 105- 110 C. I

10. The'method of making a composition of matter which comprises polymerizing vinyl chloride and vinyl acetate in the presence of rosin.

11. The product of the polymerization of vinyl chloride and vinyl acetate in the rosin.

HAROLD J. BARRETT.

presence of 

